Bis(mono-and-diperoxyoxalates) derived from dihydroperoxides and alkyl and alkylperoxy halooxalates

Abstract

A novel bis(mono- or diperoxyoxalate) composition of Structure A, <IMAGE> A and use of the novel bis(mono- or diperoxyoxalate) composition as an initiators for curing of unsaturated polyester resins and for polymerizing ethylenically unsaturated monomers are disclosed.

I claim: 
     
       1. A novel bis(mono- or diperoxyoxalate) of Structure A: ##STR42## where R 1 , R 2 , R 3  and R 4  are the same or different and are alkyl groups of 1 to 4 carbons, R 5  is a group selected from --(CH 2 ) n  --, where n is 1 to 6, --C.tbd.C--, --C.tbd.C--C.tbd.C--, 1,4-phenylene, substituted or unsubstituted 1,3-phenylene, the substituent being the structure, ##STR43## Q and Q 1  are independently selected from the group consisting of chloro, bromo, R--O, and R 6  --OO, where R is selected from the group consisting of H, a substituted or unsubstituted alkyl group of 1 to 24 carbons, substituents being one or more alkyl groups of 1 to 6 carbons, alkoxy groups of 1 to 6 carbons, aryloxy groups of 6 to 10 carbons, fluoro, chloro, bromo, carboxy and cyano, a substituted or unsubstituted alkenyl group of 3 to 12 carbons, substituents being one or more lower alkyl groups of 1 to 4 carbons, a substituted or unsubstituted aryl group of 6 to 10 carbons, substituents being one or more alkyl groups of 1 to 6 carbons, alkoxy groups of 1 to 6 carbons, aryloxy groups of 6 to 10 carbons, chloro, bromo and cyano, a substituted or unsubstituted aralkyl group of 7 to 13 carbons, substituents being one or more alkyl groups of 1 to 6 carbons, a substituted or unsubstituted cycloalkyl group of 5 to 12 carbons, a substituted or unsubstituted cycloalkyl group of 5 to 12 carbons having one or more oxygen or nitrogen atoms in the cycloalkane ring, with substituents for the cycloalkyl group being one or more lower alkyl groups of 1 to 4 carbons, a substituted or unsubstituted bicycloalkyl group of 6 to 14 carbons, with substituents being one or more lower alkyl groups of 1 to 4 carbons, a substituted or unsubstituted tricycloalkyl group of 7 to 16 carbons, with substituents being one or more lower alkyl groups of 1 to 4 carbons, and, R can additionally be structure (a), ##STR44## where R 10  is an unsubstituted alkylene group of 1 to 3 carbons or a substituted alkylene group of 1 to 3 carbons, substituents being one or more lower alkyl groups of 1 to 4 carbons, R 7  and R 8  are alkyl groups of 1 to 4 carbons, R 9  is selected from unsubstituted t-alkyl groups of 4 to 12 carbons, substituted t-alkyl groups of 4 to 12 carbons, t-cycloalkyl groups of 6 to 13 carbons, t-alkynyl groups of 5 to 9 carbons, t-aralkyl groups of 9 to 13 carbons, unsubstituted aroyl groups of 7 to 11 carbons, substituted aroyl groups of 7 to 11 carbons, where the substituent for the t-alkyl groups is a t-alkylperoxy group of 4 to 8 carbons and the substituents for the aroyl groups are one or more lower alkyl groups of 1 to 4 carbons, alkoxy groups of 1 to 4 carbons, phenyl groups, acyloxy groups of 2 to 8 carbons, t-alkylperoxycarbonyl groups of 5 to 9 carbons, fluoro, chloro or bromo, and R 9  can also be structures (b), (c) and (d) ##STR45## where x is 0 or 1, R 11  is a substituted or unsubstituted alkyl group of 1 to 18 carbons, substituents being one or more alkyl groups of 1 to 6 carbons, t-alkylperoxy groups of 4 to 8 carbons, alkoxy groups of 1 to 6 carbons, aryloxy groups of 6 to 10 carbons, hydroxy, chloro, bromo or cyano or a substituted or unsubstituted cycloalkyl group of 5 to 12 carbons or substituted or unsubstituted cycloalkyl groups of 5 to 12 carbons having one or more oxygen or nitrogen atoms in the cycloalkane ring, with substituents for the cycloalkyl groups being one or more lower alkyl groups of 1 to 4 carbons, and,   R 12  is selected from a substituted or unsubstituted alkylene group of 2 to 3 carbons, substituents being one or more lower alkyl groups of 1 to 4 carbons, or a substituted or unsubstituted 1,2-, 1,3- or 1,4-phenylene group, substituents being one or more lower alkyl groups of 1 to 4 carbons, chloro, bromo, nitro or carboxy, and,   R 13  is a lower alkyl group of 1 to 4 carbons, and, additionally, the two R 13  groups may be concatenated to form an alkylene group of 4 to 5 carbons, R 14  is a lower alkyl group of 1 to 4 carbons, R 15 , R 16  and R 17  are selected from hydrogens, alkyl groups of 1 to 8 carbons, aryl groups of 6 to 10 carbons, alkoxy groups of 1 to 8 carbons and aryloxy groups of 6 to 10 carbons, and,   R 6  is selected from an unsubstituted t-alkyl group of 4 to 12 carbons, a substituted t-alkyl group of 4 to 12 carbons, a t-cycloalkyl group of 6 to 13 carbons, a t-alkynyl group of 5 to 9 carbons, and a t-aralkyl group of 9 to 13 carbons, where the substituent for the t-alkyl group is a t-alkylperoxy group of 4 to 8 carbons.   
     
     
       2. The bis(mono- or diperoxyoxalate) compound as defined in claim 1 selected from the group consisting of: 2,5-dimethyl-2,5-di(ethoxycarbonylcarbonylperoxy)hexane, 2,5-dimethyl-2,5-di(docosyloxycarbonylcarbonylperoxy)hexane, 2,5-dimethyl-2,5-di(4-t-butylcyclohexoxycarbonylcarbonyl-peroxyl hexane, 2,5-dimethyl-2,5-di(isobornyloxycarbonylcarbonylperoxy)hexane, 2,5-dimethyl-2,5-di(neopentyloxycarbonylcarbonylperoxy)hexane, 2,5-dimethyl-2,5-di(neopentyloxycarbonylcarbonylpercoxy)-3-hexyne, 2,5-dimethyl-2,5-di(bornyloxycarbonylcarbonylperoxy)hexane, 2,5-dimethyl-2,5-di(benzyloxycarbonylcarbonylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butoxycarbonylcarbonylperoxy) hexane, 2,5-dimethyl-2,5-di(hexafluoroamyloxycarbonylcarbonylperoxy)hexane, 2,5-dimethyl-2,5-di(chlorocarbonylcarbonylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxycarbonylcarbonylperoxy)hexane, and 2,5-dimethyl-2,5-di(3-t-butylperoxy-1,3-dimethylbutoxy-carbonylcarbonylperoxy)hexane.   
     
     
       3. The bis(mono- or diperoxyoxalate) as defined in claim 1 wherein Q and Q 1  are the same and R 1 , R 2 , R 3  and R 4  are the same and are alkyl groups of 1 to 2 carbons. 
     
     
       4. The bis(mono- or diperoxyoxalate) as defined in claim 3 wherein Q and Q 1  are selected from R--O and Cl. 
     
     
       5. The bis(mono- or diperoxyoxalate) as defined in claim 4 wherein Q and Q 1  are R--O. 
     
     
       6. The bis(mono- or diperoxyoxalate) as defined in claim 5 wherein R 5  is selected from --C.tbd.C-- and --(CH 2 ) n  --, and n is 2. 
     
     
       7. The bis(mono- or diperoxyoxalate) as defined in claim 6 wherein R 5  is --(CH 2 ) n  -- and n is 2. 
     
     
       8. The bis(mono- or diperoxyoxalate) as defined in claim 7 wherein R is selected from the group consisting of H, a substituted or unsubstituted alkyl group of 1 to 22 carbons, substituents being one or more alkyl groups of 1 to 6 carbons, alkoxy groups of 1 to 6 carbons, aryloxy groups of 6 to 10 carbons, chloro, bromo, carboxy and cyano, a substituted or unsubstituted cycloalkyl group of 5 to 12 carbons, substituents being one or more lower alkyl groups of 1 to 4 carbons, a substituted or unsubstituted bicycloalkyl group of 6 to 14 carbons, with substituents being one or more lower alkyl groups of 1 to 4 carbons, and structure (a). 
     
     
       9. A process for the curing of unsaturated polyester resin compositions which comprises heating such resins in the presence of initiating amounts of the bis(mono- or diperoxyoxalate) of claim 1 at appropriate temperatures. 
     
     
       10. The process as defined in claim 9 wherein the bis(monoperoxyoxalate) is 2,5-dimethyl-2,5-di(isobornyloxycarbonylcarbonylperoxy)hexane. 
     
     
       11. A process for polymerizing ethylenically unsaturated monomers which comprises heating such monomers in the presence of initiating amounts of the bis(mono- or diperoxyoxalate) of claim 1 at appropriate temperatures. 
     
     
       12. The process as defined in claim 11 wherein the ethylenically unsaturated monomer is vinyl chloride.